The invention concerns 14.alpha.,15.alpha.- and 14.beta.,15.beta.-methylene derivatives of the estrane series, which have the following general formulae ##STR2## in which R' is hydrogen or a methyl radical; R is a hydroxyl, acetoxy, arylaminocarbonyloxy, alkylaminocarbonyloxy radical;
Z is hydrogen or a lower alkyl, or PA1 R and Z together are oxygen, PA1 Z is hydrogen or a lower alkyl; PA1 R and Z together are oxygen
and which because of their hormonal and antihormonal properties are of therapeutic importance, 3-methoxy-14.alpha.,15.alpha.- and 14.beta.,15.beta.-methylene-estra-1,3,5(10)-triene-17.alpha.- and 17.beta.-ols as well as 3-methoxy-17.alpha.-methyl-14.beta.-15.beta.-methylene-estra-1,3,5(10)-tri ene-17.beta.-ol exhibiting strong antifertility effects which particularly in the case of 3-methoxy-14.alpha.-15.alpha.-methylene-estra-1,3,5(10)-triene-17.alpha.-o l and 3-methoxy-14.beta.,15.beta.-methylene-estra-1,3,5(10)-triene-17.alpha.- and 17.beta.-ol as well as in the case of 3-methoxy-17.alpha.-methyl-14.beta.-15.beta.-methylene estra-1,3,5(10)-triene-17.beta.-ol are associated with a very favorable separation of desirable contraceptive and undesirable uterine and antigonadotrophic activities.
It is known that olefins may be methylenated by the Simmons-Smith reaction with dihalogen methanes and a zinc-copper pair or with diazomethane and zinc iodide. Also, steroid olefins were methylenated with dihalogen methanes and zinc copper. Under unfavorable steric conditions methylene addition, however, may be rendered more difficult or may be even suppressed in the case of homoallyl alcohols such as 3-hydroxy-.DELTA.5(6)-steroids. Methylene addition to the .DELTA.14-double bond has not yet been described.